Mineral oil composition



Patented Apr. 23, 1940 iTE rA'rEN'r orrlce MINERAL on. ooivmosrrron NoDrawing.

Application September 14, 1938,

Serial No. 229,876

1? Claims.

This invention has 'to do in a general way with mineral oil compositionsand is more particularly related to compositions comprised of mineraloil and a minor proportion of an added ingredient which will improve theoil in one or more important respects.

It is well known to those familiar with the art that mineral oilfractions refined for their various uses are in and of themselvesusually deficient in in one or more respects, so that their practicalutility is limited even in the particular field for which they have beenrefined. For example, mineral oil fractions refined for use aslubricants have a tendency to oxidize under conditions of use with 1.3the formation of sludge or acidic oxidation products; also the lighterfractions such as gasoline and kerosene tend to oxidize with theformation of color bodies, gum, etc. In order to prevent the formationof these products and thereby extend the useful life of the oilfraction, it is common practice to blend with such oil fractions anadditive ingredient which will have the efiect of inhibiting oxidation,such ingredients being generally known to the trade as oxidationinhibitors or sludge inhibitors, gum inhibitors, etc.

It is also the practice to add other ingredients to mineral oilfractions for the purpose of improving the oiliness characteristics andwearreducing action of such mineral oils when they 3% are used aslubricants, particularly when the oils are used for the purpose oflubricating metal surfaces which are engaged under extremely highpressures and at high rubbing speeds.

Other ingredients have been developed for the 35 purpose ofdepressingthe pour point of mineral oil fractions which have beenrefined for use as lubricants, such refinement leaving a certain amountof wax in the oil, which, without the added ingredient, would tend tocrystallize at 4o temperatures which render the oil impracticable foruse under low temperature conditions. Additive agents have also beendeveloped for improving the viscosity index of lubricating oilfractions. In the case of internal combustion en- 45 gines, particularlythose operating with high cylinder pressures, there is a decidedtendency for the ordinary lubricating oil fractions to form, under suchconditions of use, carbonaceous de- 5 posits which cause the pistonrings to become stuck in their slots and which fill the slots in the oilring or rings, thus materially reducing the efficiency of the engine.Ingredients have therefore been developed which, when added to the oil,will reduce the natural tendency of the oil to form deposits whichinterfere with the function of the piston rings. Aside from thecorrosive action which attends theformation of acidic products ofoxidation in mineral oil fractions of the lubricant range, it 5 has beendiscovered that certain types of recent- 1y, developed hard metal alloybearing metals, such as cadmium-silver alloy bearings, are attacked byingredients in certain types of oils, particularly oils of highviscosity index obtained by various methods of solvent refining. Thiscorrosive action on alloys of the above type has led to the developmentof corrosion inhibitors which may be used in solvent-refined oils toprotect such bearing metals against this corrosive action.

In the lighter mineral oil fractions. such as those used for fuelpurposes, particularly in internal combustion engines, it has been foundthat the combustion characteristics of the fuel may be controlled andimproved. by adding minor proportions of various improving agentsthereto.

The various ingredients which have been developed for use in mineral oilfractions to improve such fractions in the various respects enumeratedabove are largely specific to their particular applications, and it hastherefore been the practice to add a separate ingredient for each of theimprovements which is to be effected.

It is a primary object of the present invention to provide a mineral oilcomposition which has been improved in one or more of the variousproperties enumerated above by the incorporation therein of a smallquantity of a multifunctional compound selected from that group or classof metal-organic compounds which may be designated as the oil-soluble oroil-miscible metal salts of alkyl-substituted aryl ether acids. Morespecifically our invention contemplates as oil-improving agents theoil-miscible metal salts of alkyl-substituted aroxy aliphatic acids andalkylated aroxy-aromatic acids in which the hydrogen of the carboxylgroup or groups is substituted with metal. We have discovered that metalsalts of alkylated aryl ether acids of the general class above referredto may be added in small quantities to mineral oil fractions to formmineral oil compositions or blends superior to the unblended fractionsin one or more important respects, and the present invention, therefore,is broadly directed to a mineral oil composition containing a 50compound falling into the general class referred Our invention has as afurther and more specific objectthe provision of a viscous mineral oilfraction which has been improved in one or more of the foregoing recitedrespects by having incorporated therein a minor proportion of an oil-Iniscible metal salt of an alkylated aryl ether acid.

The oil-improving; agents contemplated by this invention may beconsidered as alkylatedxhydroxyaromatic compounds in which the hydroxylhydrogen is replaced with an organic acid groupsuch as an aromatic acidgroup or an aliphatic acid group in which acid group the carboxylhydrogen is substituted with its equivalent weight of metal. Thecompounds or products which are preferred, particularly from'astandpoint of synthesis, may be considered as alkylated hydroxyaromaticcompounds in which the hydroxyl hydrogen is replaced with an alkyl oraryl metal carboxylate group. Compounds or compositions of this type arecharacterized by the presence of an aromatic nucleus in which at leastone nuclear hydrogen has been substituted with an ether acid or an oxyacid substituent, in which substituent the carboxyl hydrogen has beenreplaced with its equivalent weight of metal. This characterizing groupmay be represented by the formula: T (O.Z.COOM) in which T represents anaromatic nucleus; and (O.Z.COOM) represents at least one ether acid oroXy acid substituent in which Z represents an aromatic or aliphaticgroup having at least one carboxyl group, the hydrogen of whichisreplaced with its equivalent weight of a metal M.

The metal salts of arylether acids of the type corresponding to thegroup represented by the above formula which are otherwise unsubstitutedare not, in general, miscible with mineral oil, and it is, therefore,important that the improving agents containing the above characterizinggroup have additional nuclear hydrogen replaced with substituents of anoil solubilizing nature. In other words, it is important that the arylnucleus T carry a substituent or substituents which will render thecomposition as a whole miscible with mineral. oil fractions. By theterms oil-miscible or oil-soluble as they are used herein, we havereference to that property of remaining uniformly dispersed in themineral oil fraction either as a true solution or as a colloidalsuspension during normal conditions of handling and use.

The improving agents contemplated by this invention are'characterized bythe presence of alkyl substituents directly or indirectly substituted inthe aryl nucleus T, and the improving agents preferred for use inviscous mineral oils are further characterized by the presence of 'alkylor aliphatic substituents in the aryl nucleus T which will give otherproperties to the composition as a whole in addition to oil-miscibility.We have found, for example, that where this aryl nucleus is substitutedwith one or more aliphatic groups corresponding to certain aliphatichydrocarbon compounds of relatively high molecular weight (such asaliphatic groups having at least. twenty carbon atoms, herein referredto as heavy alkyl groups), a com-- pound or composition can be obtainedwhich will effect marked improvement in the viscosity index and the pourpoint as well as other important properties of viscous mineral oils.

As a general proposition, therefore, it may be said that the improvingagents contemplated by this invention are metalsalts of aryl ether acidshaving the characterizing group T(O-Z-COOM) described above, in whichadditional hydrogen on the aryl nucleus T is replaced with anoilsolubilizing substituent such as a predominantly aliphatic material,suchsubstituent comprising a suflicient proportion 'of the compositionas a whole to render the same miscible with mineral oil fractions undernormal. conditions of handling and use. As a further generalization, itmay be said that at least one point on the aromatic nucleus T, andpreferably two or more points on such nucleus, are substituted withaliphatic hydrocarbon radicals or groups, such aliphatic radicals orgroups preferably being high molecular weight aliphatic derivatives orheavy alkyl groups.

The simplest type of compound satisfying the above requisites may berepresented by the formula:

in which R represents at least one aliphatic hydrocarbon radical orgroup, such group or groups preferably corresponding to relatively highmolecular weight aliphatic hydrocarbons and being attached to a mono orpoly cyclic aromatic nucleus T and in which (O-Z-COOM) is as indicatedabove.

In addition to the aliphatic or alkyl substituent R, the compounds orcompositions contemplated herein as mineral oil-improving agents mayhave additional nuclear hydrogen of the aryl nucleus T replaced withother substituents which may or may not have a solubilizing effect uponthe composition as a whole. Such a compound in its simplest 'form may berepresented by the formula:

in which R, T, and (O-Z-COOM) have the same significance indicated aboveand in which Y represents residual hydrogen of the aryl nucleus T whichmay be replaced by a radical from the group consisting of: chlorine,alkoxy, aroxy, aralkyl, alkaryl, aryl, nitro, and amino radicals orgroups. Compounds of the above general formula-type having mono, di, andhi cyclic nuclei are illustrated by the following specific formulae:

in which at least one R represents an aliphatic radical or group,preferably a heavy alkyl group,

cals or groups in which the several valences are attached to separatearomatic nuclear groups T.

Compounds of this type are included under the following general formularepresentation:

in which T and (O-Z-COOM) have the same significance indicated above; Rrepresents at least one aliphatic or alkyl radical or group, such alkylgroup or groups being attached by one valance only to at least onearomatic nucleus T, 0 representing the valence of the aliphatic radicalR", which may be one to four; Yb represents a monovalent element orgroup selected from the class identified above in connection with Y; brepresents the number of Y's and is equal to zero or a whole numbercorresponding to the valences on the nucleus T not satisfied with R and(O-Z-COOM); and n represents a whole number from one to four andindicates the total number of groups (T(O'Z'COOM)Yb) present in themolecule represented by the formula which are attached to the aliphaticgroup or groups represented by R through the valences v.

In the foregoing general formula representation III it will be seen thatthe compounds represented thereby include those materials in which allof the aliphatic substituent is monovalent (12:1 and n=1) or in whichall of the aliphatic substituent is polyvalent (v and n being equal totwo, three, or four); or since R" is defined as being at least onealiphatic radical or group and may therefore include several'suchgroups, it will be seen that this general Formula 111 is inclusive ofcompounds I having aliphatic groups or radicals of different valences(from onev to four) in the same molecule. Also it will be observed thatsince 12 may be any whole number from one to four, the number ofaromatic nuclei T in the molecule may likewise vary from one to four. Itwill be seen, therefore, that the relationship between n and v inFormula III, in its broadest aspect, is such that when n is=equal toone, 1) is equal to one; and when n is greater than one, the valence vof at least one of the its is equal to n (in 0rd to tie the severalnuclei or T's together), the valence of any'remaining R's being anywhole number equal to or less thann.

As stated above, and as will appear more fully later on from thedescription of their synthesis, these materials represented by generalFormula III may contain both monovalent and polyvalent aliphaticsubstituents. Both the polyvalent ali- Dhatic substituent and themonovalent substituent, if both are present, may be introduced in thenucleus as part of an alkylation reaction, or all or part of themonovalent aliphatic substituent' may be present in the nucleus of ahydroxyin which T and (O-Z-COOM) have the same significance as indicatedabove; R represents at least one polyvalent aliphatic radical or grouphaving a valence o of two, three, or four; Yb indicates the same groupof substituents as described above for Y; Re represents monovalent :1aliphatic radicals or groups; b represents the number of Yw's and isequal to'zero or a whole number corresponding to the valences on thenucleus T not satisfied with R (O-Z-COOM) and Re; 0 indicates the numberof Re's and is equal to zero or a whole number corresponding to thevalencebonds on the nucleus T not satis-v fied with R (O-Z-COOM) andYb'; and n represents a whole number from two to four and indicates thetotal number of the groups present in the molecule represented by theformula which are attached to the aliphatic group or groups representedby R"' through the valances v.

In the above general Formulae III and IV it will be understood thatsince R and R are aliphatic hydrocarbon radicals of the chain type andare each attached by one valence bond only to each correspondingaromatic nucleus, the valence v or v of such radical or radicals is ofnecessity never greater than the number n, which indicates the number ofaromatic nuclei in the molecule and in Formula III is always. equal toone when n equals one. Otherwise an R. or an R having a valence greaterthan the number (n or n) of aromatic nuclei would either have some ofits valence bonds unsatisfied or else would form a condensed ring orrings .by attachment at two or more points to one and the A. O.Z.CO0M

H H C "CH H II In the aboveformula the chain represents theil-solubilizing alkyl substituent (R and Yb and (O-Z-COOM) have the samesignificance as has been heretofore given to these groups.

Since group R has been defined as at leastone, it will be apparent thatthere may be more than one heavy alkyl substituent attached to thenucleus T. Such a compound, where v and n are each onev and in whichthere are two. such monovalent R groups, may be represented by thefollowing formula:

in which the chainsand the substituent characters have the samesignificance defined above;

Compounds of the type satisfying the general Formula III and thesubgeneric Formula IV inwhich R (or R f) is polyvalent and v (or v) andn (or n) are more than one and in which there is only one suchpolyvalent R group may be illustrated by the following formula, in whichthe aryl nucleus T is again indicated for illustration as beingmonocyclic:

to.z.oooM

In the above formula C, Re is a monovalent alkyl group as defined aboveunder Formula IV and is the same as monovalent'R. in Formula III.

Under this same type of compound indicated by Formula C there may alsobe more than one polyvalent R. group (represented by the chain), such acompound in which there are, for example, two polyvalent R" groups beingillustrated by the following formula, in which thercharacteriz- 'inggroups have the same significance described above under FormulaC.

1). H H B.- H H Ho --o --o --o --CH H V l H 0.Z,COOM o.z.ooo1vr 0.Z.COMY.-@-R kw-11, Yi-""' -R H H Ho --o --o --o --oH H H H H H The possiblemolecular structure of compounds in which the aryl nucleus '1- ispolycyclic will be obvious from the foregoing exemplary Formu-- E. H H HH H Ho --o --o --o --cH H H o.z.oo0M o-.z.oooM 0.Z.OO0M

Y;B. Yv--- a. in- R.

H H 110 --c --o --oH H H H- H As to the possible number of R" and (Re)groups going to make up a single molecule, this will vary with theextent to which it is desired to effect substitution of the nucleus withoilsolubilizing aliphatic groups for obtaining the desired properties inthe product and is, of course, limited by the number of valences on thearcmatic nucleus which are available for substitution. As will beapparent to those skilled in the art, the maximum possible number of R(and Re) groups which can be attached to a single aromatic nucleus willvary as the nucleus is mono or poly cyclic and also as the nucleus isotherwise substituted. It will also be app rent that available valenc'eson the nuclei may all be attached to polyvalent aliphatic substituents.

It will be understood that the oil-improving agents used in the mineraloil compositions contemplated by this invention may be pure compoundssatisfying the general Formula 111 described above with any one of thevarious mono and poly cyclic aromatic nuclei as 'I and the varioussubstituents R (or R and Y) described.

However, in manufacturing the preferred oil-improving product of thepresent invention by the preferred-method of procedure, as will appearmore fully later on, the final oil-improving product obtained isnormally or usually a mixture of different compounds corresponding todifferent values of n and v and to different numbers of aliphatic groupsR".

As has been emphasized hereinabove, it is important that theoil-improving agents as represented by general Formulae III and IV havenuclear hydrogen in the aromatic nucleus 'I' substituted withpredominantly aliphatic material which comprises a sufficient proportionof the composition as a whole to render the same miscible with themineral. oil fraction in which the improving agent is used under normalconditions of handling and use. It appears from the results of ourresearch that there is a critical range in the degree of alkylation ofthese im- ,the alkylated hydroxyaromatic compound from which thealkylated aryl ether acid salt is derived should not exceed a certainpercentage of such alkylated hydroxyaromatic composition as a whole.This critical range of alkylation may be roughly expressed as the ratioby weight of (T(OH))n to RV(T(OH))1:. I

The degree of alkylation and the critical ranges within which operativeand preferred compounds can. be obtained may also be expressed as thenumber of carbon atoms contained in the aliphatic substituents for eacharyl nucleus in a given molecule or molecular structure.

The critical range in the degree of alkylation of the aryl nucleus inthe improving agents contemplated herein may vary with: (a) the mineraloil fraction in which the improving agent is to be used; (b the arylnucleus T (monoor polycyclic); (c) the hydroxyl content of the arylnucleus from which the final product is obtained (monoor polyhydric);-(d) the character of aliphatic material comprising the substituent(straight or branched chain) (e) monoor polysubstitution of the arylnucleus; and (f) other substituents on the nucleus T, which may be ofpositive or negative or of neutral solubilizing activity.

In general, it may be said that a polycyclic nucleus appears to requirea higher degree of alkylation than a monocyclic nucleus; that apolyhydric nucleus requires a higher degree of alkylaand that tion thana monohydric nucleus; branched chain aliphatic substituents have asomewhat greater solubilizing action than straight chain solubilizingsubstituents.

In view of the foregoing variables, it would be impracticable andprobably misleading to attempt to give an expression and figure whichwould indicate accurately the proper ratio of hydroxyaromaticconstituent to the alkylated hydroxyaromatic constituent which wouldexpress a degree of aliphatic substitution satisfying all cases takingthese variables into account. As a guide for preparing these improvingagents, however, our research indicates that for a product having pourdepressing and V. I. improving properties in addition to other valuableproperties the ratio ment inseveralimportant properties. The imof (T(OZ-COOM)) to R'('I'(O-Z-COOM)) expressed as:

should not be greater than about .20 when the weight of thehydroiwaromatic nucleus or component (T(OH))n is expressed in terms ofits chemically equivalent weight of phenol (C6H5OH) However, for mereoil-solubility with inhibition of oxidation we have found that thisratio may be raised to about 0.6 by substituting the nucleus withbranched chain aliphatic groups. In general, it may be said that in thepreferred improving agents contemplated herein the ratio by weight ofthe hydroxyaromatic component in the product to the correspondingalkylated hydroxyaromatic nucleus or component therein should not begreater than about twenty parts by weight of the former to about 100parts by weight of the latter, or about twenty per cent, when the weightof the hydroxyaromatic nucleus or component is expressed in terms of itschemically equivalent weight of phenol. It will be observed that theratio as represented by the Formula VII does not take into account anyother substituent in the nucleus than the aliphatic substituents and thehydroxyl group or groups; but since the aliphatic substituent isprimarily relied upon in the agents contemplated herein as thesolubilizing substituent, it is believed that the foregoing expressionand limits will serve as a working guide for the preparation ofoil-soluble materials and the preferred multi-functional materials.

As stated above, the degree of alkylation may also be expressed by thenumber of carbon atoms contained in the aliphatic substituent for agiven hydroxyaromatic nucleus T. As a; general guide here it may be saidthat the aliphatic substituents represented by 1'1. in the above generalFormula III should, for the preferred multifunctional materialscontemplated herein, contain a total of atleast twenty-five carbon atomsfor each aromatic nucleus T.

The ratio oftwenty per cent, which we may term the phenolic ratio,represents what we consider a maximum figure for the preferred productscontemplated herein, and in generalit will be found that for thespreferred multifunctional products this figure will be lower, the actualratio, of course, being dependent upon the variable factors enumeratedabove. For example, as will later apear, an improving agent of. thepreferred type in which the aliphatic substituent is derived frompetroleum wax '(a predominantly straight chain aliphatic hydrocarbon ofat least twenty carbon atoms) and in which the aromatic nucleus wasderived from phenol otherwise unsubstituted may have a phenolic ratio,as expressed above, not substantially greater than about sixteen percent.

A further general guide for the synthesis of the prefered improvingagents for viscous oils is to alkylate the aromatic nucleus so that itis polysubstituted. with aliphatic hydrocarbon radicals or groupspreferably of relatively high molecular weight.

As has been previously indicated, .it is one of the primary objects ofthe invention to provide an oil-improving agent which will havemultifunctional improving activity in a mineral oil. Our researchindicates that compounds satisfying the requisites of general FormulaIII above may be blended in minor proportions with mineral 01]fractions, particularly of the viscous or lubricating oil type, toeffect marked improveprovement effected may be varied somewhat withaliphatic substituent, petroleum wax and allphatic hydrocarbons ofsimilar characteristics such as ester wax, for example, giving productswhich eflectamarked improvement in viscosity index and pour point inaddition to other properties to be hereinafter pointed out. Theeifectiveness may also be varied with other substituents in the arylnucleus for example, alkoxy groups contribute to solubility-and theproperties of the agents may also be varied with the character of themetal substituent in the carboxyl group.

In general, it appears that the oil-miscible salt of any metalsatisfying the requisites of Formula III above will act to inhibitoxidation in mineral oils and-reduce the formation of harmful oxidationproducts. Certain of the metals, such, for example, as copper, lead, andzinc, may serve to increase the load-carrying capacity of lubricatingoils.

Procedures whereby the oil-improving agents contemplated by thisinvention in which the oxyacid substituent is derived from a fatty acidcan be prepared, may be broadly described as follows:

First the hydroxyl hydrogen in an alkylated hydroxyaromatic compound issubstituted with an alkali metal to form an alkylated aryl alkali metaloxide:

in which Cl-Z-COOM represents the sodium salt of a chlor aliphatic acid,Z' in this case being an aliphatic group. This reaction may also beexpressed as follows:

(12) R (T(oM )Yb)n-|-C1(CnH2n) -000M R"(T(0- (CnHan) -COOM+MC1 Anotherdesirable procedure for the formation of alkali metal salts of alkylatedaryl ether acids in which the ether acid substituent is an aliphaticacid derivative consists in reacting anester of the chlor aliphatic acidinstead of the alkali salt of the aliphatic acid with the alkylated arylmetal oxide, followed by saponification of the product according to thefollowing equations:

Alkali metal ether acid salts formed in the foregoing exemplaryprocedures may be obtained with the alkali metal salts of anychlor-aliphatic acid such 'as sodium, chlor-acetate, butyrate,heptylate, palmitate, stearate, etc. It is preferred that the reactionsbe carried out in the presence of a non-aqueous medium.

The ether acid salts in which the ether acid or oxyacid substituents isderived from an allphatic acid are considered preferred from thestandpoint of synthesis, but it is to be understood that similar saltsmay be obtained in which the group -Z-CO'OM in the ether acidsubstituent '(O-Z-COOM) represents the residue of an aromatic acid salt.Alkali salts of diaryl ether acids of this character can be synthesizedby reacting an alkyl-substituted aryl alkali metal oxide with abrom-aryl alkali carboxylate in the presence of a small percentage ofpowdered copper as a catalyst, the reaction-mixture being heated toabout 400 F. This reaction may be represented by the following equation:

in which MX indicates a salt of the metal M which is soluble in asolvent for the ether acid salt in which the corresponding alkali metalsalt M X is insoluble.

Metal salts of alkylated aryl ether acids can also be formed by firstneutralizing the alkali metal salt with mineral acid to form the etheracid, followed by water washing to purify the product, and then reactingthe anhydrous acid with the alcoholate of the desired metal according tothe following equation:

in which Alk OM) indicates an alcoholate of the metal M. v

The details of the foregoing procedure; will be discussed hereinafterwith specific examples.

The metal substituents in the ether acid group attached to the aroxynucleus of the improving agents described herein may be broadlyclassified as the metals belonging to the silver, copper. tin, aluminum,iron, alkali and alkaline earth analytical groups, which include:silver, mercury, lead, and thallium; bismuth, copper, and cadmium;arsenic, antimony, and tin; iron, cobalt, nickel, and manganese; barium,calcium, strontium, and magnesium; and sodium, potassium, and lithium,respectively. Other desirable metals include: titanium, cerium, thorium,vanadium, molybdenum, tungsten, uranium, and platinum.

The general reactions described and illustrated above, have shown analkylated or an aliphaticsubstituted hydroxyaromatic compound as thestarting material. Compounds of this nature, which satisfy therequirements of high alkylation for the preferred improving agentsdiscussed above, or mixtures of such compounds can be readily preparedby alkylating a monoor polycyclic, monoor poly-hydric, substituted orunsubstituted hydroxyaromatic compound with aliphatic compounds orpredominantly aliphatic materials.

The starting material for the hydroxyaromatic constituent in thealkylation reaction to obtain an alkylated hydroxyaromatic product R(T(oH)Yb)n, in which Yb, if present, is residual hydrogen, may be amonoor poly-cyclic hydroxy-aromatic compound otherwise unsubstituted; orsuch compounds containing alkyl substituents; or in certain specialcases (to be hereinafter described) the starting material may beanalkyl-aryl ether or an aralkyl-aryl ether. For obtaining an alkylatedhydroxyaromatic product containing a Y substituent, in addition to or inplace of residual hydrogen, the starting material for thehydroxyaromatic constituent may be .a monoor poly-cyclic hydroxyaromaticcompound in which part of the nuclear hydrogen is substituted with amember or members of the group consisting chlorine, hydroxy, alkoxy,aroxy, aryl, alkaryl k nd aralkyl groups.

Examples of the droxyaromatic compounds which may be used as startingmaterial for the alkylation reaction are: phenol, resorcinol, hy-.droquinone, catechol, cresol, xyl enol, .hydroxydiphenyl, benzylphenol,phenyl-ethyl-phenol, phenol resins, methyl-hydroxydiphenyl, alpha andbeta naphthol, alpha and beta methyl naphthol, tolyl naphthol, xylylnaphthol, benzyl naphthol, anthranol, phenyl methyl naphthol,phenanthrol, anisole, beta naphthyl methyl ether, chlorphenol, and thelike. Preference in general is to the monohydroxy phenols otherwiseunsubstituted, particular preference being given to phenol and alpha andbeta naphthol.

The alkylation of the hydroxyaromatic compound may be accomplished invarious ways, such as by a Friedel-Crafts synthesis, using a halogenatedaliphatic hydrocarbon, or by reaction with unsaturated high molecularweight aliphatic compounds or higher alcohols in the presence of H2SO4as a catalyst.

We have found the Friedel-Crafts type of alkylation reaction to beparticularly adapted to the step of preparing the alkylatedhydroxyaromatic compounds from which the improving agents describedherein are synthesized because it affords a convenient means forcontrolling the degree of alkylation and obtaining the desired phenolicratio for use in the preferred mineral oil compositions contemplated bythis invention.

In this reaction an appropriate mono or polychlorine-substitutedaliphatic compound or material is reacted with the desiredhydroxyaromatic compound in the presence of a catalytic amount ofaluminum chloride. Pure or substantially pure monoorpoly-chlorine-substituted aliphatic compounds may be used. However, aswill be readily understood by those skilled in the art, since it isusually very diflicult to prepare or obtain high molecular weightaliphatic hydrocarbons in a pure or substantially pure state and sinceit is equally difilcult to prepare the chlorine (or other halogen)substitution products of such hydrocarbons in a pure or substantiallypure state, we prefer to employ a mixture of such hydrocarbons, such asa suitable petroleum fraction, as the starting material for ourpreferred improving agents, converting it into a mixture of differentchlorine (or other halide) substitution products by any suitable methodfor use in the alkylation step. In general, it may be said that the highmolecular weight aliphatic hydrocarbons contemplated by this inventionas preferred sources for the-alkyl or aliphatic substituent R, inFormula III above may be pure or mixed compounds typified by those whichcharacterize the heavier products of petroleum, such as heavy petroleumoils of the lubricant type, petrolatum, and crystalline petroleum wax orother compounds or materials which will result in relatively long chainaliphatic substituents. Special preference is given to petroleum wax ofmelting point not substantially less than about I20 F. Such speciallypreferred aliphatic hyirocarbon materials commonly have molecularweights of about 350 and have at least twenty :arbon atoms in theirmolecules.

As stated above, the Friedel-Orafts synthesis lfl'ords a convenientmeans of controlling the degree of alkylation of the product. This isaccomplished by controlling: (a) the chlorinaion of the aliphatichydrocarbon and (b) the 'eacting proportions of the chlorinatedaliphatic iydrocarbon and the hydroxyaromatic comound used in theFriedel-Crafts reaction. As well known to those skilled in the art, theeplacement of nuclear hydrogen in the hydroxy- Lrom'atic compound withan aliphatic group is, n the Friedel-Craits synthesis, eiiected by re-.ction of such nuclear hydrogen with chlorine n the chlorinatedaliphatic compound, the subtitution being efiected with evolution ofH01. t will thus be seen that the number of chlorine ubstituents in achlorinated aliphatic compound orresponds to the number of valences (vin genral Formula III) which will be satisfied by or ttached tohydroxvaromaticnuclei in the prodlct of the reaction. For example, in areaction where a quantity of pure monochloraliphatic lydrocarboncontaining say three atomic proortions of chlorine is reacted with onemolecular roportion of hydroxyaromatic compound, the reulting alkylatedproduct, RF(T(OH)Yb) n, is one :1 which 2: and n are equal to one andthere re three aliphatic groups R" attached to one .ucleus T. On theother hand,assuming a rection in which a quantity of puretrichloralihatic hydrocarbon containing three atomic proortions ofchlorine is reacted with one molecun' proportion of hydroxyaromaticcompound. he product would be one in which 0 and n of eneral Formula IIIare each equal to three, and he solubilizing action of a singlealiphatic group ould be distributed among three nuclear hyroxyaromaticgroups. It is due to this latter ondition that we consider it preferablethat the umber of valence bonds 1) (in R" of Formulae II, etc.) bemaintained within the range of rom one to four hereinahove specified. Inother ords, it appears that the required oil-solubiliz- 1g andoil-improving action of the aliphatic ubstituent R", particularly wherethe aliphatic ubstituent is a wax derivative and the agent to be usedfor multifunctional activity in v'isous oils, is not obtained withmaterials preominantly comprised of a-compound or comounds R(T(OZ'COOM)Yb)n (Formula III) in hich uand 11. are greater than four.Hence, Jr use in the Friedel-Crafts reaction thechlorrated highmolecular weight aliphatic material could be a compound, or should bepredominant- Y comprised of compounds in which the chlorine antent isnot greater than a tetrachlor .comound.

As will be readily apparent to those skilled in ac art, the chlorinationof an aliphatic maarial such as a liquid petroleum fraction or arystalline petroleum wax will normally or usually esult in a mixture ofmonoand poly-chloralihatic hydrocarbon compounds. Consequently, 1eproduct of a Friedel-Crafts reaction between 1011 chlorinated materialand a hydroxyaroia'tic compound will be a mixture of diiferent ompoundscorresponding to difierent values of and n in the formula R"(T(0I-)Yb)nand 1e final 'alkylated aryl ether acid salt derived iereirom accordingto the reactions of equations b", d, etc., above will likewise be amixture of compounds corresponding to different values of n and v ingeneral Formula III. It will be understood, therefore, that the specificvalues for v and n in the above formula, as well as the formula itself,relate to the diiferent specific compounds present in such a mixturewhich charhereinabove.

The above-mentioned ratio of hydroxyaromatic component to thecorresponding alkylated hydroxyaromatic component I ))i\ in which thehydroxyaromatic component is calculated as phenol and which is thereforeherein referred to as the phenol content or phenolic ratio, is usuallycalculated from the weight of -th'e hydroxyaromatic compound used up inthe all-aviation reaction and from the total weight of alkylatedcompound resulting from such alkylation reaction, as will be readilyunderstood by those skilled in the art.

For example, when the Friedel-Crafts synthesis is used for alkylation,the aliphatic hydrocarbon materialis first chlorinated until the weightof chlorine'absorbed indicates that the average composition of thechlorinated product corresponds roughly (in the case of a high molecularweight aliphatic hydrocarbon) to say a dichloraliphatic hydrocarbon.Such a product will, of course, contain some mono and. trlchlorcompounds and probably some tetrachlor compounds. The reactingproportions (based on atomic proportions of chlorine to one mole of.hydroxyaromatic compound) are then selected so that the theoreticalproduct of the Friedel- Crafts reaction will give the approximatephenolic ratio desired. After the Friedel-Crafts reaction andpurification of the product the Weight of alir phatic material in thechlorinated aliphatic starting material is subtracted from the weight ofthe alkylated or aliphatic-substituted product to obtain the weight ofhydroxyaromatic material ((T(OI-I) )n) actually combined or used up inthe alkylation synthesis. From this value and the weight of thealkylated product (R"(T(0H))n) the phenolic ratio or phenol content canbe readily calculated. If there are other substituents 1 (Yb) on thehydroxyaromatic nucleus in addition to the monoor poly-valent aliphaticgroups, a deduction should be made for them before calculating thephenolic ratio, an operation which will be apparent to those skilled inthe art.

In theforegoing description of the Friedel- Craits alkylation reactionwe have referred to a hydroxyaromatic compound as a starting material.This same reaction may be used with an alkyl-aryl ether or anaralkyl-aryl ether which undergoes a substantial rearrangement duringFriedel-Crafts alkylation to form an alkylated' hydroxyaromatlccompoundin which the alkyl group of the ether replaces one of thenuclearhydrogen atoms.

In the event it is desired to obtain a product R"(T(O-Z-COOM) Yb) nwhich contains an alkoxy group as the substituent-Yb, it is preferablethat the alkylation be effected with a'"hydroxyaro- 'maticcompoundcontainingsuch' alkoxy or aroxy group as 'a substituent and ahigh molecular weight unsaturated aliphatic hydrocarbon (such aspolymerized isobutylenef dodecyl ene, tetradecylene, octadecylene,melene, etc.) or a higher alcohol (such as cetylalcohol,-myricyl'alcohol, ceryl alcohol, octadecylalcohol, etc.) 'using H2804 as acatalyst. By this procedure, the hydroxyaromatic ether can be alkylatedwithout substantial rearrangement taking place. As an alternativeprocedure, polyhydric phenols can be alkylated by reaction with alcoholsor unsaturates or by Friedel-Crafts reaction followed by substitution ofone hydroxyl hydrogen with a low molecular weight alkyl group. Incarrying out this latter procedure, the alkylated polyhydric phenol istreated with an alkali alcoholate to introduce alkali metal into the OHgroup followed with the desired alkyl halide, whereby the substitutionis effected.

When it is desired to obtain a nitro or amino group as the substituentYb" in general Formula III, the hydroxy aromatic compounds are.alkylated when free of nitro or amino groups, and such alkylation isfollowed by nitration of the alkylated compound to introduce the nitrosubstituent.

The amino group can be obtained by reduction of the nitro group.

PREPARATION OF WAX-SUBSTITUTED PHENYL E'I'HER ACID SALTS 1) ALKYLarroNor PHENOL after which chlorine isbubbled therethrough' until the wax hasabsorbed from-sixteen per cent to twenty per cent of chlorine, suchproduct having an average composition between a monochlor wax and adichlor wax or corresponding roughly -to-a dichlor wax. Preferably thechlorination is continued until'about one-fifth the weight of thechlorwax formed is chlorine. A quantity of chlorwax thus obtained,containing three atomic proportions of chlorine, is heated to atemperature varying from just above ts melting point to not over F., andone mole of phenol (CsHaOH) is admixed therewit The mixture is heated toabout 150 F., and a quantity of anhydrous aluminum chloridecorresponding to about three per cent of the weight of chlorwaxin themixture is slowly added to the mixture with active stirring. The rate ofaddition of the aluminum chloride should be sufficiently slow to avoidviolent foaming, and during such .addition the temperature should beheld at about 150 F. After the aluminum chloride has been added, thetemperature of the mixture -may be increased slowly over a period offrom fifteen to twentyfive minutes to 'a' temperature of about 250 F.and then should be more-slowly increased to around 300 F.-350 F. Tocontrol the evblution of 1101 gas the temperature of the mixture ispreferably raised from 250 F. to 300 E 350? F. at a rate ofapproximately one degree per minute, the whole heating operationoccupying approximately two hours from the time'of adding the' aluminumchloride. If the emission of HCl gas has not ceased when the finaltemperature is reached, 'the mixture may be held at 350 F. for I a shorttime to allow completion of the reaction. 'But, to avoid possiblecracking of the wax, the mixture should not be heated appreciably above350 F., nor should it be held at that temperature for any extendedlength of time. 1

It is impo'tant that allunreacted or nonalkylated hydioxyaromaticmaterial (phenol) remaining after'the alkylation reaction be removed.Such removal'can be efiected generally by water-washing, but it ispreferable to treai the water-washed product with super-heatec steam,thereby insuring complete removal of the unreacted material andaccomplishing the drying of the product in the same operation.

The wax-substituted phenol thus obtainec may be characterized by thegeneral formula R (T(OH)Yb) n, in which R. represents at leas onealiphatic group or radical characteristic 0 paraffin wax having avalence v of from on to four; T represents a monocyclic aromatic nucleus; Yb represents residual hydrogen, b be ing a number correspondingto the number 0 valences on the nucleus T not satisfied by R and (OI-I);and n is a number from one to fou corresponding to the valences v on thealiphatir group or groups R' which are satisfied by the nu clear groupor groups T(OH) Yb.

4 wax-substituted phenol prepared accordln "to the above procedure, inwhich a quantity 0 chlorwax containing three atomic proportions ochlorine (twenty per cent chlorine in the chlor wax) is reacted with onemole of phenol, may, fo brevity herein, be designated as wax-phenc(3-20). Parenthetical expressions of this typ (A-B) will be usedhereinafter in connectio: with the alkylated hydroxyaromatic compound todesignate (A) the number of atomic propor tions of chlorine inchloraliphatic material re acted with one mole'of hydroxyaromatic compound in the Friedel-Crafts reaction, and (B the chlorine content of thechlor-aliphatic mate rial. In the above example A=3 and B=20. Thisamedesignation will also apply to the arox metal salt carboxylatederivatives.

Wax-phenol (3-20) as obtained by the 'abov procedure had a phenolcontent or a phenolic ra tio of about sixteen per cent. Our research indicates that this phenolic ratio in the neighbor hood of sixteen orseventeen per cent may 11 considered as representing about the maximuifor satisfactory miscibility and multifunction: activity in viscous oilsof the aroxy carboxylal metal salt derivatives of alkylated hydroxyarcmatic compounds in which the alkyl substituent: derived from wax and thehydroxyaromatic con stituent is derived from"phenol (Cd-BOH). Ei fectiveoil-improving agents can, however. be ok tained from wax-phenol(3- 16),in which tl: phenol content or phenolic ratio is in the neigr borhood oftwelve or thirteen per cent.

(2) Foamxrron or Wax-Sunsrrrurm ALKALI ALKALINE EAa'rn Mrrmr. Pursue Asan example of this step in the preparatic of our oil-improving agents,wax-substituted S( .dium phenate can be prepared by the reactionwax-phenol with metallic sodium in the presem of a non-oxidizing gas.The-reaction mixture.

heated at 500 F; during a two-hour period wit rapid stirring "to producefinely divided sodiu:

and thereby accelerate the reaction. The prc portions of reactants whichwere used in prepai completion of the reaction.

ing a wax-substituted alkali metal phenate according to the aboveprocedure were:

- Grams Wax-phenol (13.2 per cent combined phenol content) 500 Sodium orequivalent amount of potassium 16 It will be understood, of course. thatother reactions may be employed to efiect the alkali metal substitution.

(3) FORMATION OF ETHER Acln SALTS FROM VAX- ALKALI METAL PHENATE (a)24.7 grams of monochloracetic acid in cc. of absolute ethyl alcohol wasconverted to sodium chloracetate by adding dropwise a standard alcoholsolution of sodium hydroxide, maintaining the temperature of thereaction mixture below 100 F. This sodium chloracetate mixture was thenadded to a solution of 200 grams of wax-phenol (3-16) as the wax-sodiumphenate,

in 600 grams of mineral oil (Say. Vis. 244 sec. at F.), and the reactionmixture was held at F. during a two-hour period to form thewaxsubstituted phenoxy sodium acetate. By diluting the mixturesufllciently with Stoddard solvent or other appropriate diluent, themixture can be centrifuged to remove reaction salts, thereafter removingthe light diluent by distillation to obtain the pure product.

The wax-phenoxy acetic acid used in certain of the hereinafter describedprocedures can be obtained by neutralizing the reaction mixture, beforepurification, with hydrochloric acid. The free acid is purified bywater-washing the product to remove reaction salts and drying to give aconcentrated .mineral oil blend of the finished product.

(b) 200 grams of wax-phenoxy-sodium acetate (Ii-16) in mineral oilsolution was reacted with 17.68 grams of zinc chloride by addingdropwise an alcoholic solution of zinc chloride to the sodium ether acidsalt (Wax-phenoxy sodium ace-, tate) and holding the temperature of thereaction mixture at a temperature of F. during a two-hour period tocomplete the reaction. The mixture may be diluted with Stoddard solventor other suitable diluent and the wax-phenoxyzinc acetate (3-16)obtained can be purified by water-washing and distilling to remove thediluent.

c) Cobaltous ethylate was formed by adding an alcoholic solution of 16.7grams anhydrous cobaltous chloride to sodium ethylate (5.97 gm. Nacontent.) Without purification, the cobaltous ethylate was added to amineral oil blend containing 200 grams of wax-phenoxy-acetic acid 3-16)and the reaction mixture was heated to 350 F. and held at thattemperature for a two-hour period during which the alcohol distilled offwith The wax-phenoxy cobaltous acetate thus formed can be purified'bysettling and centrifuging or water-washing to remove reaction salts.

(d) The same general. procedures described above have been used inpreparing wax-phenoxyacetates from wax-phenol (3-19) having a combinedphenol content or phenolic ratio of 15.7 per cent. Here the proportionsof reactants for making the wax-sodium phenate were 200 grams ofwax-phenol (15.7 per cent combined phenol) in 800 grams of mineral oiland eight grams of sodium as the sodium ethylate. 200 grams ofwax-phenoxy acetic acid prepared from the wax phenate obtained above wasreacted with 76.8

grams of sodium as sodium ethylate to form the wax-phenoxy-sodiumacetate (3-19).

Wax-substituted aryl ether acid salts of the general character describedabove can be prepared from other wax-substituted hydroxyaromaticcompounds, either monoor poly-cyclic and substituted or unsubstituted,such, for example, as wax-naphthol (319) having a combined naphtholcontent of sixteen per cent and equivalent phenol content or phenolicratio of 9.7 per cent. They may also be obtained with other alkylsubstituents than petroleum wax, although, as indicated above, alkylatedhydrocarbons of the wax type (having at least twenty carbon atoms) arepreferred because of the multifunctional activity of their products. Itis also emphasized that the invention is not limited to productsobtained from acetic acid as a source for the ether. acid substituentbut that any chloraliphatic acid (as the alkali salt thereof) may beused to obtain various alkyl chains or groups,

in the ether acid or oxy-acid substituent. Also, as we have previouslypointed out, the waxphenoxy-aromatic carboxylate types of salts arecontemplated herein. Such compounds can best be prepared from awax-alkali phenate and brom-aromatj c acid, the reaction being carriedout at elevated temperature in the presence of be broadly characterizedas oil-miscible metal salts of alkylated aroxy-carboxylic acids in whichpart of the hydrogenin the aroxy nucleus is replaced with a mineraloil-solubilizing substituent. Compounds of this general type may befurther characterized as oil-miscible, metal salts of alkylated oralkyl-substituted aryl ether acids in which the carboxyl hydrogen hasbeen substituted with its equivalent weight of metal; also as alkylatedhydroxyaromatic compounds in which the hydroxyl hydrogen has beensubstituted with an organic acid salt radical or group, it beingunderstood that the terms alkyl and a1kylated are used herein in a broadsense to include polyatomic or polyvalent, as well as monovalentaliphatic radicals or groups, and that an organic acid salt radical orgroup is an aliphatic, alicyclic, or aromatic carboxylic acid residuehaving one carbon valence-available for attachment to the, oxygen of ahydroxyaromatic compound to forman aryl ether linkage.

To demonstrate the efiectiveness of compounds or products of the typedescribed above in the mineral oil compositions contemplated by thisinvention, we have conducted several comparative tests, the, results ofwhich are listed below, with representativev mineral oils alone. andwith the same oils blended with the improving agents contemplated bythis invention.

POUR POINT DEPRESSION Table I A. S. T. M. pour tests Depressant blendedwith motor oil of on on and on blends Saybolt viscosity of 244 sec.at'130 F.

F. F. F. Wax-phenoxy-zinc acetate (3-16) +20 -20 10Wax-phenoxy-cobaltous acetate (3-16) +20 -20 15 Wax-phenoxy-sodiumacetate (3-19) +20 25 -10 Wax-phenoxy-cobaltous acetate (3-19) +20 15 10Wax-phenoxy-cobaltous benzoate (3-16). +20 20 -15 V. I. IMIPROVENIENTAnother property of the mineral oil compositions contemplated by thisinvention which has been investigated and found to have been improved bymetal salts of certain of the alkylated aryl-ether acids is theviscosity index. The effectiveness of the wax-aryl ether acid salts asV. I. improvers is demonstrated by the data in Table II below. Inobtaining this data the viscosity index was obtained in the conventionalmanner from the Saybolt viscosity of the oil and the oil blends at F.and 210 F. The oil used was a viscous mineral oil of the lubricant type.

OPERATION TEST In addition to the foregoing tests we have also madetests of an oil and an oil blend containing a representative improvingagent of the type contemplated by this invention to determine thecomparative behavior of the unblended oil and the improved oil underactual operating conditions. The test was carried out in a singlecylinder 0. F. R. engine. The engine was operated continuously over atime interval of twenty-eight hours, with the cooling medium held at atemperature of about 390 F., at a speed of 1200 R. P. M., which isequivalent to a road speed of about twenty-five miles per hour. The oiltemperature was held at about F. during the test.

The oil used in this test was a lubricating oil stock of 120 secondsSaybolt Universal viscosity at 210 F., and the conditions observed atthe end of the test were (a) the extent to which the piston rings werestuck, b) the extent to which the slots in the oil rings were filledwith deposit, (0) the amount of carbonaceous deposits in the oil, and(d)' the acidity or neutralization number as indicated by the resultstabulated below.

(N. N.) ,of the oil at the end of the test. The oil indicated as A inTable III below is the unblended oil, and oil 18" is the same oilcontaining of wax-phenoxy-cobaltous acetate. The results of this testindicate a substantial inhibition against the deleterious effects ofoxidation.

Table III Ring condition 1 Oil Degrees stuck gg gfig 325 32;: N. N.

A. 360 360 360 360 50 50 0 17. 25 l 1. 7 B l. 0 0 0 0 O 0 0 0 6. 53 0. 4

Table IV below shows the effectiveness of amyl phenoxy cobaltous acetateas an inhibitor. The oil indicated as A was blended with one-third percent of this inhibitor to give oil B.

From the foregoing results it will be apparent that metal salts ofalkylated aryl ether acids of the type contemplated by this inventionare efiective oil-improving agents and the preferred wax-substitutedproducts are characterized by the fact that they have, through thepresence of the wax-substituted aryl nucleus and the metal substituents,multifunctional activity. Although we do not wish to be bound in anyregard by any theory as to the function which the metal substituentshave, it is believed that such sub'stituents act by promoting thepreferential oxidation of the alkylated aryl-ether acid molecule,thereby taking up active oxygen and acting as a direct antioxidant; alsoby acting as a peptizing agent on any sludge that is formed in theoxidation" of the oil; and in the event an alkali or alkaline earthmetal is present as the metal substituent, the salts act by neutralizingstrong acids in the oil, particularly sulfur acids such as may be formedby oxidation. The improved properties obtained and the degree ofimprovement in a particular property may be varied with the metalsubstituents, the aryl constituents, and the degree of alkylation of thearyl nucleus.

As to the degree of alkylation, it is important that the aryl nucleus besufficiently alkylated to provide a final product which is soluble ormiscible in the particular mineral oil fraction with which it is to beblended; that is, one which will remain uniformly dispersed in the oilin suflicient amount to effect the desired improvement under normalconditions of storage and use.

The amount of improving agent used may be varied, depending upon themineral oil or the mineral oil fraction with which it is blended and theproperties desired in the final oil composition. The alkylated arylether acid salts of the type described herein may be used in amountsranging from one-sixteenth per cent to ten per cent, and in generalcompositions of the desired improved properties may be obtained withthese improving agents in amounts .of from one-sixteenth per cent to twoper cent..

It is to be understood that while we have described certain preferredprocedures which may be followed in the preparation of the alkylatedaryl-ether acid salts used as improving agents in the mineral oilcompositions contemplated by this invention and have referred to variousrepresentative constituents in these improving agents, such proceduresand examples have been used for illustrative purposes only. Theinvention, therefore, is not to be considered as limited by-the specificexamples given but includes within its scope such changes andmodifications as fairly come within the spirit of the appended claims.

We claim:

1. An improved mineral oil composition comprising a viscous mineral oilfraction having admixed therewith a minor proportion of an oilmisciblemetal salt of an aryl ether acid in which part of the hydrogen on thearyl nucleus has been substituted with predominantly aliphatic organicmaterial, said last-mentioned substituent comprising a suflicientproportion of the aryl ether acid saltv to render said salt misciblewith said oil under normal conditions of handling and use.

2. An improved mineral oil composition comprising a mineral oil havingadmixed therewith in minor proportion: an oil-miscible metal salt of awax-substituted aroxy-aliphatic carboxylic acid.

- 3. An improved mineral oil composition comprising a viscous mineraloil fraction having admixed therewith in minor proportion: anoilmiscible metal salt of an alkyl-substituted aryl ether-carboxylicacid.

4. An improved mineral oil composition comprising a viscous mineral oilfraction having admixed therewith in minor proportion: an oil- .misciblemetal salt of an alkyl-substituted aryluent is a high molecular weightaliphatic hydrocarbon group and in which the 'aryl nucleus ispoly-substituted with said alkyl substituent.

'7. An improved mineral oil composition comprising aviscous mineral oilfraction having admixed therewith a minor proportion of an oil-misciblemetal salt of an alkyl-substituted phenoxy-aliphatic carboxylic acid.

8. An improved mineral oil composition comprising a. viscous mineral oilfraction having admixed therewith a minor proportion of an oil-misciblemetal salt of any alkyl-substituted naphthoxyealiphatic carboxylic acid.

9. Animproved mineral oil composition comprising a mineral oil havingadmixed therewith a minorproportion of an oil-miscible metal salt of awax-substituted phenoxy-aliphatic carboxylic acid.

10. An improved mineral oil composition com-. prising a mineral oilhaving admixed therewith a minor proportion of an oil-miscible metalsalt of a wax-substituted naphthoxy-aliphatic carboxylic acid.

11. An improved .mineral oil composition comprising a mineral oil havingadmixed therewith a minor proportion of an oil-miscible metal salt of awax-substituted phenoxy-aliphatic carboxylic acid in which the metalsubstituent is selected from the group consisting of sodium, zinc, andcobalt.

12. An improved mineral oil composition comprising a viscous mineral oilfraction having admixed, therewith a minor proportion, from aboutone-sixteenth per cent .to about ten per cent, of an oil-miscible metalsalt of an alkylsubstituted aryl-ether carboxylic acid.

cent of an oil-miscible metal salt of an alkylsubstituted aryl-ethercarboxylic acid in which said alkyl substituent is derived frompetroleum wax.

14. A composition of matter comprising a mineral oil fraction and inadmixture therewith a minor proportion of an oil-miscible metalorganiccompound having the general formula: R (T(O'ZCOOM)Yb)n in which: Trepresents an aromatic nucleus} (O-Z-COOM) represents at least one etheracid salt subs'tituent attached to T and wherein 0 represents oxygen, Zrepresents an aliphatic or an aromatic group and COOM represents atleast one carboxyl group, the hydrogen thereof being replaced by itsequivalent weight of a metal M; R represents at least one aliphatic.group having a valence v of from one to four, and attached by onevalence only to at least one nucleus T; Yb. represents a monovalentradical attached to T and selected from the group consistingof residualhydrogen, andchlorine, alkoxy, aroxy, aralkyl, alkaryl, aryl, nitro, andamino radicals; b represents the number of Ybs and is equal. to zero ora whole number corresponding to the valences on the nucleus T notsatisfied with R and (O-Z-COOM) and n is a whole number-from one tofour, the substituent R comprising a suflicient proportion of themetalorganic compound as a Whole to render the same miscible withsaidmineral oil under normal conditions of handling and use.

15. A composition of matter comprising a mineral oil fraction and inadmixture therewith a minor proportion of an oil-miscible metalorganiccompound having the general formula: R (T(O-Z-COOM)Y1,).in which: Trepresents an aromatic nucleus; (O-Z-CQOM) represents at least one etheracid salt substituent attached to T and wherein 0 represents oxygen, Zrepresents an aliphatic or an aromatic group and COOM represents atleast one carboxyl group the hydrogen thereof being replaced by itsequivalent weight of a metal M; R. represents at least one aliphaticgroup having a valence v of one to four, and attached by one valenceonly to at least one nucleus T; Yb represents .a monovalent radicalattached to T and selected from the group consisting of residualhydrogen, and chlorine, alkoxy, aroxy, aralkyl, alkaryl, aryl, nitro,and amino radicals; b represents the number of Yes and is equal to sewera whole number corresponding to the valences on the nucleus T notsatisfied with R. and (O-Z-COOM) and n is a whole number from one tofour, the total number of carbon atoms in all of the aliphatic groupstaken together in said metalorganic compound being not less than abouttwenty-five for each nucleus T.

16. A composition of matter comprising a mineral oil fraction and inadmixture therewith a minor proportion of an oil-miscible metalorganiccompound having the'general formula: R (T(O'Z'COOM)Yb)n in which; Trepresents an aromatic nucleus; (O-Z-COOM) represents at least one etheracid salt substituent attached to T and wherein 0 represents oxygen, Zrepresents an aliphatic or an aromatic group and COOM represents atleast one carboxyl group the hydrogen thereof being replaced by itsequivalent weight of a metal M; R represents at least one aliphaticgroup having a valence v of one to four and attached by one valence bondonly to at least one nucleus T; Yb represents a monovalent radicalattached to T and selected from the group consisting of residualhydrogen,

.and chlorine, alkoxy, aroxy, aralkyl, alkaryl, aryl,

nitro, and amino radicals; b represents the number of Ybs and is equalto zero or' a whole number corresponding to the valences on the nucleusT not satisfied with R and (O-Z-COOM); andn is a whole number from oneto four, the ratio of (T(O'Z'COOM))12 to R (T(O-Z-C0OM))11 in saidmetalorganic compound expressed as attached to T and wherein 0represents oxygen, Z represents an aliphatic or an aromatic group andCOOM represents at least one carboxyl group, the hydrogen of which isreplaced with its equivalent weight of a metal M; R"' represents atleast one polyvalent aliphatic hydrocarbon group of at least twentycarbon atoms having a valence v of from two to four; Yb represents amonovalent radical attached to T and selected from the group consistingof residual hydrogen, chlorine, alkoxy, aroxy, alkaryl, aralkyl, aryl,nitro, and amino radicals; b represents the number of Yb"s and is equalto zero or a whole number corresponding to the valences on the nucleus Tnot satisfied by R', (O-Z-COOM) or Re; Re rep? resents monovalentaliphatic radicals; c represents the number of Rcs and is equal to zeroor a whole number corresponding to the valences on the nucleus T notsatisfied with R (O-Z-COOM) and Yb; and n is a whole number from two tofour. l

' ORLAND M. REIFF.

FERDINAND P. OTTO.

cERTIErcAT-E 0F CORRECTION.

Patent No. 2,198,292.

April 25, 19!;0.

ORLAND n. REIFF, ET AL.

It is hereby certified that error appears in the printed specificationof the above numbered patent requiring correction as follows: Page 10,first column, line 20, in the right-hand column in the heading of Table1, for

"-1/2 read -1/ 2";

and that the said Letters Patent shouldbe read with thisvcorrectiontherein that the same may conform to the record ofthe case in the PatentOffice.

Signed and sealed this 18th day of March, A. D. l9lil.

(Seal) Henry Van Arsdale, Acting Commissioner of Patents.

represents at least one ether acid salt substituent l A; ,..l.

CERTIFICATE OF CORRECTION.

Patent No. 2,19 ,292, Apr-i125, 191w.

' 0mm) :1. REIFF, ET AL.

It is hereby certified that error appears in the printed Specificationof the above numbered patent requiring correction as follows: Page 10,first 601m, line 20; in the right-hand oolumn inthe heading of Table 1,for "1/2 read --1/3 and that the said Letters Patent shouldbe read withthis correction therein that the same may conform to the record ofthecase in the Patent Office.

Signed and sealed this 18th day of March, A. D. 19in.

Henry Van Arsdale, 7 Acting Commissioner of Patents.

